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The effect of lowered groundwater surface tension using alcohols and surfactants, and increased viscosity using a thickener on the performance of the air sparging (AS) process was investigated, and...

The surfactant-enhanced gas sparging process designed to specifically target the source zone of an organic contaminant in an aquifer with minimal usage of injected additives was investigated using a physical model. Aqueous solutions of the anionic surfactant Sodium dodecylbenzne sulfonate (SDBS) and/or the thickener Sodium carboxymethylcellulose (SCMC) were applied in a contaminated horizontal layer in the simulated laboratory aquifer model followed by gas sparging. Fluorescein sodium salt (FSS) was added to the SDBS/SCMC solutions and represented the organic contaminant. Air and ozone were injected to generate gas sparging. A modified surfactant-enhanced ozone sparging method was also tested by applying additional air venting ports installed in the aquifer above the gas injection zone. Both non-aqueous phase liquid (NAPL) and water-dissolved TCA were applied to the SDBS-applied region to evaluate the removal of contaminants during gas sparging. A significant expansion of the de-saturated zone for the SDBS-applied region was observed during air sparging. During ozone sparging, the fluorescence by FSS in the SDBS-applied layer disappeared over a much wider range than that of the control experiment. SCMC application enhanced the performance of the SDBS-applied gas sparging process. The TCA mass removed by volatilization during air sparging from the SDBS-applied layer was 2.3 times the application in the absence of SDBS. Among five regions of injected NAPL contamination located above the single gas injection port, and during 2 h of ozone sparging, with SDBS applied, more than 50% of fluorescence in the NAPL was removed, whereas under the same conditions with no SDBS applied, less than 30% was removed. Diverted gas flow through the venting ports installed in the aquifer model induced a horizontally expanded oxidative reaction zone during ozone sparging. This study demonstrates enhanced gas sparging performance for the removal of contaminants from the aquifer with limited usage of additives applied specifically to the source zone.

The effects of surface-tension and/or viscosity changes in groundwater on the remedial performance of air sparging for heterogeneous aquifers were investigated. The study used a one-dimensional (1-D) column and a two-dimensional (2-D) flow-chamber aquifer model. To introduce a heterogeneous setting, the middle part of the model was packed with a finer soil [LKZ, low hydraulic conductivity (K) zone]. Fluorescein sodium salt was used at 200 mg/L for all experiments as a surrogate contaminant. For the 1-D column experiments, the rate of fluorescence decay in the LKZ during surfactant-enhanced air sparging (SEAS) was significantly higher than during the standard air sparing (AS) process without additives; the area of fluorescence loss, measured after 17 h of air sparging (including ozone), was double and triple that of the conventional AS process, for SEAS without thickener (SEAS1) and SEAS with thickener (SEAS2), respectively. Experimental results using the 2-D chamber also confirmed the enhanced air intrusion into the LKZ during the SEAS process. The air fluxes through the LKZ increased by 47 and 103% for the SEAS1 and SEAS2 compared to AS, respectively; and 79 and 90% of fluorescence disappeared in the LKZ during ozone injection for SEAS1 and SEAS2, respectively, whereas only 10% disappeared for AS during the 3-h experimental period. The findings of this study indicate that the AS process, at low surface tension and increased groundwater viscosity may be a viable alternative to the conventional AS process for aquifers of heterogeneous hydrogeological formations.

This study examines the effect of controlled groundwater flow paths induced by hydraulic barriers on the removal of NAPL constituent. An aqueous solution of thickener [0.05% (w/v) sodium carboxymethyl cellulose, SCMC] was continuously injected into a horizontally set two-dimensional physical model (sand-packed), forming aqueous plume(s) of high viscosity. The water flux at the down gradient of the model was measured using a flux tracer (n-octanol) and passive flux meter (PFM, packs of granular activated carbon). A non-reactive tracer (pentafluorobenzoic acid, PFBA) was used to identify the plume of high viscosity (hydraulic barrier) and ambient groundwater. When the barrier of high viscosity was formed, the plume was separated from the background water with little mixing, which was confirmed by the concentration profile of PFBA; whereas, the measured flux of ambient groundwater showed a distinctive distribution, due to the hydraulic barrier. When two barriers were set, the ambient water flux was enhanced in the middle, and the removal rate of PCE from the non-aqueous phase liquid (NAPL), measured by PFM, was found to improve by 26% during three hours of water flushing. When an aqueous solution of surfactant [0.37% (w/v), sodium dodecyl sulfate, SDS] was applied instead of water into the domain with two barriers set around the NAPL-contaminated spot, the removal of PCE from the NAPL increased by 101% for a three-hour time period. Based on the observations made in this study, hydraulic barriers formed by continuous injection of thickener solution change the flow direction of groundwater, and may increase the flux of groundwater (or aqueous solution of remediation agent) through a NAPL-contaminated region, improving the removal of NAPL.

The effects of controlled air flow paths during air sparging on the removal of volatile organic compounds were examined in this study using a two-dimensional bench-scale physical model. An aqueous solution of sodium carboxymethylcellulose (SCMC), which is a thickener, was used to increase the resistance of water to displacement by injected air in a region around the targeted zone. At the same time, an aqueous solution of sodium dodecylbenzene sulfonate (SDBS), which is a surfactant, was used to reduce the air entry pressure to enhance the air flow through the targeted region. Trichloroethene (TCE), dissolved in water, was used to represent an aqueous phase volatile organic compound (VOC). A binary mixture of perchloroethene (PCE) and n-hexane was also used as a nonaqeous phase liquid (NAPL). Controlled air flow through the source zone, achieved by emplacing a high viscosity aqueous solution into a region surrounding the TCE-impacted zone, resulted in increased TCE removal from 23.0% (control) to 38.2% during a 2.5h period. When the air flow was focused on the targeted source zone of aqueous phase TCE (by decreasing the surface tension within the source zone and its vicinity by 28 dyn/cm, no SCMC applied), the mass removal of TCE was enhanced to 41.3% during the same time period. With SCMC and SDBS applied simultaneously around and beneath a NAPL source zone, respectively, the NAPL components were found to be removed more effectively over a period of 8.2h than the sparging experiment with no additives applied; 84.6% of PCE and 94.0% of n-hexane were removed for the controlled air flow path experiments (with both SCMC and SDBS applied) compared to 52.7% (PCE) and 74.0% (n-hexane) removal for the control experiment (no additives applied). Based on the experimental observations made in this study, applying a viscous aqueous solution around the source zone and a surfactant solution in and near the source zone, the air flow was focused through the targeted contaminant zone, enhancing the removal of VOCs from either an aqueous phase or a NAPL phase.

Aqueous solutions of micro-nano bubbles (MNBs) containing ozone gas were injected through a NAPL-contaminated glass bead column. The glass column (15 cm × 2.5 cm) was packed with glass beads: the first 12 cm was packed with coarse glass beads while much finer glass beads were used to pack the remaining 3.0 cm of the column. Decane was used as the representative NAPL, to which an oil-soluble fluorescence tracer was added. The fluorescence tracer was considered as a constituent of the NAPL that readily reacts with ozone. Air and ozone-containing oxygen were used to generate MNB solutions, and injected through the column. In addition, H2O2 was introduced to the O3-containing MNB (O3-MNB) solution to investigate the effect of hydroxyl free radicals on the NAPL removal. An ozone gas sparging experiment was also conducted for comparison. After 72 h of O3-MNB application, a significant mass of n-decane (27.6% of the initial mass applied) was removed from the column. H2O2 injection into the column during O3-MNB application was effective in increasing the n-decane mass removal by 22%, compared to the O3–MNB experiment. The rate of NAPL removal during O3-MNB flushing was significant, although slower than ozone sparging. During O3-MNB application, fast decay of fluorescence was observed; whereas, during co-injection of H2O2 and O3-MNB solutions, only a slight change in the fluorescence was observed. This indicates that oxidative degradation of NAPL during H2O2 and O3-MNB injection takes place only at the NAPL-water interface due to the reactivity of hydroxyl free radical, whereas ozone diffusion into NAPL induced the decay of the fluorescence tracer in the bulk NAPL. The removal characteristics during MNB application and ozone gas sparging were investigated based on the analysis of NAPL using mass spectrophotometer. When O3-MNB and H2O2 were co-injected, only n-decane was detected in the NAPL; while when O3-MNB was used for flushing, oxidative products were found in the NAPL. More hydrophilic compounds were found in the NAPL after ozone sparging. This implies different removal mechanisms depending on the kind of oxidation agent, and the state of oxidizing fluid. Based on the findings in this study, the application of O3-MNB could be a feasible option for cleaning up NAPL-contaminated aquifers.

Neutrophil extracellular traps (NETs) are fibrous networks which protrude from the membranes of activated neutrophils. NETs are found in a variety of conditions such as infection, malignancy, atherosclerosis, and autoimmune diseases including rheumatoid arthritis (RA), systemic lupus erythematosus (SLE), anti-neutrophil cytoplasmic antibodies (ANCA)-associated vasculitis (AAV), psoriasis, and gout. Studies suggest that an imbalance between "NETosis," which is a process by which NETs are formed, and NET degradation may be associated with autoimmune diseases. Neutrophils, interleukin-8, ANCA and other inflammatory molecules are considered to play a key role in NET formation. Prolonged exposure to NETs-related cascades is associated with autoimmunity and increases the chance of systemic organ damage. In this review, we discuss the roles of various inflammatory molecules in relation to NETs. We also describe the role of NETs in the pathogenesis of autoimmune diseases and discuss the possibility of using targeted therapies directed to NETs and associated molecules to treat autoimmune diseases.

The effect of groundwater viscosity control on the performance of surfactant-enhanced air sparging (SEAS) was investigated using 1- and 2-dimensional (1-D and 2-D) bench-scale physical models. The viscosity of groundwater was controlled by a thickener, sodium carboxymethylcellulose (SCMC), while an anionic surfactant, sodium dodecylbenzene sulfonate (SDBS), was used to control the surface tension of groundwater. When resident DI water was displaced with a SCMC solution (500 mg/L), a SDBS solution (200 mg/L), and a solution with both SCMC (500 mg/L) and SDBS (200 mg/L), the air saturation for sand-packed columns achieved by air sparging increased by 9.5%, 128%, and 154%, respectively, (compared to that of the DI water-saturated column). When the resident water contained SCMC, the minimum air pressure necessary for air sparging processes increased, which is considered to be responsible for the increased air saturation. The extent of the sparging influence zone achieved during the air sparging process using the 2-D model was also affected by viscosity control. Larger sparging influence zones (de-saturated zone due to air injection) were observed for the air sparging processes using the 2-D model initially saturated with high-viscosity solutions, than those without a thickener in the aqueous solution. The enhanced air saturations using SCMC for the 1-D air sparging experiment improved the degradative performance of gaseous oxidation agent (ozone) during air sparging, as measured by the disappearance of fluorescence (fluorescein sodium salt). Based on the experimental evidence generated in this study, the addition of a thickener in the aqueous solution prior to air sparging increased the degree of air saturation and the sparging influence zone, and enhanced the remedial potential of SEAS for contaminated aquifers.

Because iron-based materials that are used for the permeable reactive barrier systems come in various shapes, sizes, and with various surface properties depending on the manufacturing sources, their reductive powers vary in a wide spectrum. A new experimental procedure to evaluate the reductive power of iron material was developed in this study. Tri-iodide (I3(-)) was used as the representative oxidizing agent that reacts with zero-valent iron (ZVI). Three iron-based materials (two scraps, two powders) and four chlorinated chemicals [perchloroethene (PCE), trichloroethene (TCE), 1,1,1-trichloroethane (TCA), and pentachlorophenol (PCP)] were used in this study. Redox reactions were conducted in glass vials containing aqueous solutions of chlorinated compounds or tri-iodide with known masses of iron material. After a predetermined reaction time each vial was opened and the solution was analyzed for the concentration of reduced compound. The apparent rate contant (k(i)(obs)) of iodine reduction reaction with ZVIs was found to be proportional to that (k(c)(obs)) of chlorinated contaminant. The surface area-normalized reduction rate constants (k(c)(nor)) for contaminants and tri-iodide (k(i)(nor)) were also proportional to each other. The ratio of rate constants, K(nor) (= k(c)(nor)/k(i)(nor)) was estimated for each contaminant; 3.29 × 10(-7), 5.86 × 10(-7), 6.70 × 10(-7), and 7.87 × 10(-10) M, for PCE, TCE, TCA, and PCP, respectively. The results of this study suggest that the reductive power of ZVI materials can be standardized using tri-iodide, and thus, can provide a good reference for the quantitative assessment of the reactivity of metallic reducing agents of environmental interest including ZVIs.

Capillary fringe divides the groundwater and the vadose zone controlling the diffusive mass transfer of contaminants and gases. The thickness of capillary fringe is of great importance for the rate of contaminant mass transfer across the capillary fringe. Application of surface active chemicals including surfactants and alcohol-based products into the subsurface environment changes the surface tension of the aqueous phase, which in turn, affects the thickness of the capillary fringe. In this study, a bench-scale model was used to assess the quantitative relationship between the surface tension and the thickness of the capillary fringe. An anionic surfactant (Sodium dodecylbenzene sulfonate, SDBS) and an aqueous solution of ethanol were used to control the surface tension of the groundwater. It was found that the thickness of the capillary fringe is directly proportional to the surface tension. The air entry pressures measured by the Tempe Pressure Cell at different surface tensions using SDBS (200 mg/L) and ethanol (20%, v/v) solutions were in good agreement with the thicknesses of the capillary fringe measured by the model. A simple method to correct the conventional Brooks-Corey model for estimating the air entry pressure was also presented.

In this laboratory study, the changes in gas-exposed perchloroethene (PCE) saturation in sand during a PCE removal process were measured using gaseous tracers. The flux of fresh air through a glass column packed with PCEcontaminated, partially water-saturated sand drove the removal of PCE from the column. During the removal of PCE, methane, n-pentane, difluoromethane and chloroform were used as the non-reactive, PCE-partitioning, water-partitioning, and PCE and water-partitioning tracers, respectively. N-pentane was used to detect the PCE fraction exposed to the mobile gas. At water saturation of 0.11, only 65% of the PCE was found to be exposed to the mobile gas prior to the removal of PCE, as calculated from the n-pentane retardation factor. More PCE than that detected by n-pentane was depleted from the column due to volatilization through the aqueous phase. However, the ratio of gas-exposed to total PCE decreased on the removal of PCE, implying gas-exposed PCE was preferentially removed by vaporization. These results suggest that the water-insoluble, PCE-partitioning tracer (n-pentane in this study), along with other tracers, can be used to investigate the changes in fluid (including nonaqueous phase liquid) saturation and the removal mechanism during the remediation process.

Surfactant-enhanced air sparging (SEAS) was evaluated in this laboratory-scale study to assess: (i) the removal efficiency of volatile contaminant from an aquifer model contrasted to conventional air sparging; and (ii) the effect of mass removal of dense non-aqueous phase liquid (DNAPL) during air sparging on the changes in aqueous flux of dissolved DNAPL. We conducted sparging experiments to remove perchloroethene (PCE) sources from laboratory flow chambers packed with sand. PCE was emplaced in rectangular zones at three locations within the flow chamber. The resident water was supplemented with the anionic surfactant, sodium dodecylbenzene sulfonate (SDBS), to reduce the surface tension of water, and then sparged with nitrogen gas at a constant flow rate of 0.12 L/min. It was found that SEAS was significantly more efficient than conventional air sparging for removing PCE. For SEAS, about 78% and 75% of total PCE mass was depleted from the flow chamber at a surface tension of 52.2 dynes/cm (350 mg/L SDBS) and 63.1 dynes/cm (150 mg/L SDBS), respectively, whereas only 38% was removed at 72.5 dyne/cm (no SDBS added). Before and after sparging, PCE mass flux in the aqueous phase during steady water flow through the chamber was measured in the flow chambers. Post-SEAS PCE fluxes were reduced, but not in direct proportion to the reduction in PCE mass.

The effect of changing water content on the air-water mass transfer kinetics of volatile organic compounds (VOCs) during gas transport in unsaturated sand was investigated. The kinetics of VOC adsorption at the air-water interface from the gas phase was explored using n-decane, whereas methylene chloride was used to examine the effect of air-water partitioning. Methane was used as the nonreactive tracer in VOC transport experiments conducted using a sand column installed in a gas chromatography system. The longitudinal dispersion of methane, estimated from methane breakthrough curve (BTC), was found to be constant in the water content range (0.07 to 0.18) examined in this study at a constant pore-gas velocity (v g ), whereas an inverse proportionality between the longitudinal dispersion and V g was observed. The BTCs for methane and n-decane, measured at constant v g , were fairly symmetric, indicating that both gas diffusion and adsorption at air-water interfaces do not produce nonequilibrium transport. The shape of the methylene chloride BTC was gradually distorted at a constant v g as water content increased. Fitting methylene chloride BTCs with a modified two-region model showed that the water partitioning becomes more rate-limited as water content increases. The overall mass transfer coefficient for water partitioning of methylene chloride was found to be a direct function of specific air-water interfacial area.

The objectives of this study are to design an optimal electro-enhanced permeable reactive barrier (E2PRB) system for the remediation of trichloroethylene (TCE)-contaminated water using zero valent iron (ZVI) and direct current (DC) and to investigate the mechanisms responsible for TCE degradation in different ZVI-DC configurations. A series of column experiments was conducted to evaluate the effect of different arrangements of electrodes and ZVI barriers in the column on the TCE removal capacity (RC). In twelve different combinations of ZVI and/or DC application in the test columns, the rate of reductive dechlorination of TCE was improved up to six times with simultaneous application of ZVI and DC compared to that using ZVI only. The most effective arrangement of electrode and ZVI for TCE removal was the column set with ZVI and a cathode installed at the down gradient. Based on the electrokinetic study for the column systems with only DC input, single acid front movement could explain different RCs. An enhanced dechlorination rate of TCE using E2PRB systems, compared to a conventional PRB system, was observed, and is considered to be attributed to more electron sources: (1) external DC, (2) electrolysis of water, (3) oxidation of ZVI, (4) oxidation of dissolved Fe2+, (5) oxidation of molecular hydrogen at the cathode, and (6) oxidation of Fe2+ in mineral precipitates. Each of these electron sources was evaluated for their potential influencing the TCE RC through the electron competition model and energy consumption. A strong correlation between the quantity of electrons generated, RC, and the energy-effectiveness was found.

Knowledge of the gas transport of volatile organic compounds (VOCs) through unsaturated soils is important for understanding the fate of these contaminants. However, studies have not been performed for examining the retardation of VOCs, based on quantitative analyses of processes contributing to retardation as the function of water content during gas flow through unsaturated soils. No investigations have evaluated whether different factors that contribute to VOC retardation during gas transport have an additive effect, such that the sum of different effects can be used to predict overall transport velocity. A series of gas transport experiments was conducted in a soil column over a range of water contents, using a soil with low organic carbon content (approximately 0.1%), and tetrachloroethene (PCE) and 1,1,1-trichloroethane (TCA) as representative VOCs. Three phase-partitioning processes (partitioning into soil water, adsorption at the soil particles, adsorption at the air-water interface) were evaluated independently. The sum of retardation effects from these processes was then compared with the observed VOC retardation factors. Measured retardation factors for PCE and TCA were in good agreement with those predicted over the range of water contents (0.02-0.24) examined in this study, supporting the additive nature of different phase-partitioning processes for the gas transport of VOCs in soils. Also, the relative contribution of each phase-partitioning process to the total retardation of VOCs during gas transport was a strong function of water content.

A toluene degrading microorganism, Pseudomonas putida type A1, was isolated and enriched to treat toluene vapor in a hollow fiber membrane bioreactor. Prior to the membrane reactor experiments, a set of batch experiments using this microorganism was conducted to examine the effect of oxygen levels on the microbial activity. It was found that a low oxygen level does limit the degradation rate of toluene. A hydrophobic hollow fiber module was developed for biological degradation of toluene vapor with enhanced oxygen transfer capabilities. A hydrophobic polyethylene microfiltration hollow fiber membrane bioreactor showed that toluene removal efficiencies were consistently kept in the range of 86–97% at the loads of 0.85–4.3 kg Tol./m 3 day for 150 days. The result showed that a hollow fiber membrane bioreactor system would be a useful choice for treating air emissions containing volatile organic compounds (VOC).

Air injected into an aquifer during air sparging normally flows upward according to the pressure gradients and buoyancy, and the direction of air flow depends on the natural hydrogeologic setting. In this study, a new method for controlling air flow paths in the saturated zone during air sparging processes is presented. Two hydrodynamic parameters, viscosity and surface tension of the aqueous phase in the aquifer, were altered using appropriate water-soluble reagents distributed before initiating air sparging. Increased viscosity retarded the travel velocity of the air front during air sparging by modifying the viscosity ratio. Using a one-dimensional column packed with water-saturated sand, the velocity of air intrusion into the saturated region under a constant pressure gradient was inversely proportional to the viscosity of the aqueous solution. The air flow direction, and thus the air flux distribution was measured using gaseous flux meters placed at the sand surface during air sparging experiments using both two-, and three-dimensional physical models. Air flow was found to be influenced by the presence of an aqueous patch of high viscosity or suppressed surface tension in the aquifer. Air flow was selective through the low-surface tension (46.5 dyn/cm) region, whereas an aqueous patch of high viscosity (2.77 cP) was as an effective air flow barrier. Formation of a low-surface tension region in the target contaminated zone in the aquifer, before the air sparging process is inaugurated, may induce air flow through the target zone maximizing the contaminant removal efficiency of the injected air. In contrast, a region with high viscosity in the air sparging influence zone may minimize air flow through the region prohibiting the region from de-saturating.

Laboratory experiments were conducted employing gas chromatographic techniques to evaluate the gaseous transport of volatile organic chemicals (VOCs) in water-unsaturated soil columns as influenced by interfacial (air-water) adsorption and water partitioning. VOCs [methylene chloride, tetrachloroethene (PCE), 1,1,1-trichloroethane (TCA), ethyl-benzene, p-xylene, chlorobenzene] with different water-partitioning and interfacial adsorption coefficients (air-water) were used to evaluate the theoretical basis of using these coefficients to predict the retardation factors (Rt) observed during gaseous transport. A loamy sand from Dover Air Force Base, DE, and a commercial sand were used as the column packing material to assess the effect of grain size on the air-water interfacial area (ai) and retardation at different water saturations (Sw). The ai were measured using n-alkanes. At low Sw, interfacial adsorption contributed most to the retardation for all VOCs during gaseous transport in the Dover soil which has little sorption capacity for the VOCs. As Sw increased, the fraction of Rt attributed to interfacial adsorption decreased, while that due to water partitioning increased for all of the VOCs used for this study. For the sand, with a more uniform grain-size distribution than the Dover soil, the contribution of air-water interfacial adsorption to the Rt of a VOC (p-xylene) was not as significant as that for the Dover soil due to small ai. The fractions of Rt attributed to interfacial adsorption and water partitioning were quantified. The observed Rt for the VOCs agreed well with those predicted based on the sorption coefficients and the quantities of sorption domains (Sw, ai).

Several innovative tracer techniques have been introduced during the past 5 years for enhanced characterization of the “source zones” at sites contaminated with non-aqueous phase liquid (NAPL) wastes. These tracer techniques allow for an in situ estimation of domain-averaged values and spatial patterns for NAPL saturation ( S n ), NAPL–water interfacial area ( a nw ), and bio-geochemical reactivity ( k s ) within the target test zone. The tracer tests can be used to evaluate the spatial patterns in these parameters, both before and after implementing some in situ technique for site cleanup, in order to evaluate the effectiveness of remediation achieved and the possible impacts of the cleanup technology on hydrodynamic and bio-geochemical processes. Here, we review the theoretical and experimental basis for these tracer methods, present selected examples of recent field-scale applications, and examine their reliability.

A series of gaseous miscible displacement experiments were conducted to estimate specific air-water interfacial areas (a{sub i}) and water contents in an unsaturated sand column. A straight-chain hydrocarbon (h-decane) was used as the gaseous interfacial tracer and methylene chloride and chloroform were used as the water-partitioning gaseous tracers. A gas chromatographic technique was employed for the tracer experiments conducted at room temperature using nitrogen as the mobile phase and water as the immobile liquid. Tracer experiments covered a water saturation (S{sub w}) range of 1.5 to 56%. The largest a{sub i} value, measured at the lowest S{sub w} (1.5%), was somewhat smaller than the solid surface area as determined using the nitrogen-sorption technique. As S{sub w} increased, a{sub i} values decreased exponentially to {approximately}80 cm{sup 2} cm{sup {minus}3} at S{sub w} of 56%. Within a limited S{sub w} range (0.29 < S{sub w} < 0.55), where both aqueous and gaseous interfacial tracer data were measured, the a{sub i} values measured using a gaseous tracer (n-decane) were 2 to 3 times larger than those measured in a previous study using an aqueous interfacial tracer (sodium dodecylbenzene sulfonate [SDBS]). The velocity of the air-water interface was estimated to be between 23 andmore » 36% of the bulk pore-water velocity. The water contents measured using water-partitioning tracers were within {+-}5% of those based on gravimetric measurements.« less

Miscible displacement experiments were conducted using sodium dodecylbenzenesulfonate (SDBS) and cetylpyridinium chloride (CPC) as interfacial tracers to measure non-aqueous phase liquid (NAPL)–water interfacial areas (anw) in columns packed with silanized glass beads which were coated with either n-decane or perchloroethylene (PCE). The consistency of the interfacial tracer technique was evaluated by showing that: (1) anw values measured with two tracers for two NAPLs were similar; (2) the interfacial adsorption isotherm estimated from the surfactant retardation factors was comparable to that predicted from interfacial tension data and the Gibbs adsorption equation; and (3) the measured anw values were comparable with those estimated from a simple geometrical analysis of the solid surface area of the glass beads of known size and shape.

We investigated in laboratory column experiments, the aqueous-phase transport of four n-alcohols (n-hexanol−n-nonanol), three chlorinated aromatic compounds (chlorobenzene, o-dichlorobenzene, and o-chlorophenol), and two alkylbenzenes (ethylbenzene and p-xylene) in a water-unsaturated porous medium (sand). The influence of gas-phase partitioning and interfacial adsorption on solute retardation during steady unsaturated water flow was evalu ated over a range of water contents. Air−water interfacial adsorption was a significant factor for the retardation of n-alcohols. For example, nearly 90% of the measured retardation of n-nonanol could be attributed to interfacial adsorption at a water saturation of 34%. Aromatic compounds used in this study were not significantly affected by adsorption at the air−water interface because of both low air−water interfacial area (0−50 cm2/cm3) generated in the unsaturated porous medium and the small interfacial−adsorption coefficients. Instead, gas-phase partitioning was th...

The effective specific air-water interfacial area (a¯i) in a sand-packed column was measured at several water saturations (Sw) using a surface-reactive tracer (sodium dodecylbenzene sulfonate (SDBS)) and a nonreactive tracer (bromide). Miscible displacement experiments were conducted under steady water flow conditions to quantify the retardation of SDBS resulting from its adsorption onto the air-water interface in a sand-packed column. A consistent trend of increased retardation of SDBS compared with the nonreactive tracer, bromide, was observed with decreasing Sw. The data for air-water surface tension measured at various SDBS concentrations were interpreted using the Gibbs model to estimate the required adsorption parameters. The retardation factors (Rt) for SDBS breakthrough curves were then used in combination with the estimated SDBS adsorption coefficient to calculate the a¯i values at different Sw. For the range of experimental conditions employed in this study, the retardation factor for SDBS ranged from Rt = 1.00 at Sw = 1.00 (Rt < 1 due to SDBS sorption on sand) to Rt = 3.44 at Sw = 0.29 (which corresponds to a¯i = 46 cm2/c/m3). These values are in agreement with theoretical predictions and recently published data. Improvements needed to overcome the experimental limitations of the presented method are also discussed.

An innovative surfactant-enhanced ozone sparging (SEOS) technique was developed in this study. The synergistic effect of simultaneous surfactant and ozone application on the removal of organic contaminants in an aquifer during air sparging was investigated. Using laboratory-scale one- and two-dimensional physical models packed with water-saturated sand, air sparging and ozone sparging were implemented either at high or low level surface tension of the groundwater. A water-dissolved chemical (fluorescein sodium salt) and a nonaqueous phase liquid (n-decane) were used as the representative contaminants. Sodium dodecylbenzene sulfonate was used for sparging experiments at low level surface tension. Ozone sparging at low surface tension (SEOS) was found to be the most efficient process for the removal of organic chemicals, among AS (air sparging at high surface tension), SEAS (surfactant-enhanced air sparging, air sparging at low surface tension), and OS (ozone sparging at high surface tension), based on the results from a one-dimensional column study. Two-dimensional model experiments also showed that SEOS is more efficient than conventional AS processes. The increased air saturation and sparging influence zone achieved by surfactant application, and the oxidative power of ozone are responsible for the enhanced removal of contaminants from the aquifer. Considering that the application of conventional AS is limited to volatile contaminants, and that OS has a very narrow influence zone, SEOS can be an useful option for the removal of contaminants of low vapor pressures from an expanded zone of influence.

In this laboratory study, an experimental method was developed for the quantitative analyses of gas fluxes in soil during advective air flow. One-dimensional column and two- and three-dimensional flow chamber models were used in this study. For the air flux measurement, n-octane vapor was used as a tracer, and it was introduced in the air flow entering the physical models. The tracer (n-octane) in the gas effluent from the models was captured for a finite period of time using a pack of activated carbon, which then was analyzed for the mass of n-octane. The air flux was calculated based on the mass of n-octane captured by the activated carbon and the inflow concentration. The measured air fluxes are in good agreement with the actual values for one- and two-dimensional model experiments. Using both the two- and three-dimensional models, the distribution of the air flux at the soil surface was measured. The distribution of the air flux was found to be affected by the depth of the saturated zone. The flux and flux distribution of a volatile contaminant (perchloroethene) was also measured by using the two-dimensional model. Quantitative information of both air and contaminant flux may be very beneficial for analyzing the performance of gas-driven subsurface remediation processes including soil vapor extraction and air sparging.

In this laboratory study, a new experimental method involving the use of a set of four gaseous tracers, was developed for measuring the NAPL saturation directly accessible to the mobile gas as well as the total NAPL saturation in unsaturated sand. One tracer with low water solubility (n-pentane) was used as the tracerthat partitions into NAPL directly accessible to the mobile gas, and another (chloroform)tracer with moderate water solubility and NAPL-partitioning, was selected for detecting total NAPL saturation. Helium and difluoromethane were used as the nonreactive and water-partitioning tracers, respectively. A saturated hydrocarbon, n-decane, was used as NAPL. Column experiments were conducted attwo water saturations (Sw = 0.68 and 0.16). The total NAPL saturation and NAPL saturation not directly accessible to the mobile gas were also successfully measured using the combined results of tracer experiments. At Sw = 0.68, only 28% of the total NAPL was detected by n-pentane, whereas 87% of the total NAPL was accessible to n-pentane at Sw = 0.16, implying more NAPL was accessible to the mobile gas phase at lower water saturation.

Reduction in the surface tension of groundwater, prior to air sparging for removal of volatile organic contaminant from aquifer, can greatly enhance the air content and the extent of influence when air sparging is implemented. However, detailed information on the functional relationship between water saturation, air-water contact area induced by air sparging and the surface tension of water has not been available. In this study, the influence of adding water-soluble anionic surfactant (sodium dodecyl benzene sulfonate) into groundwater before air sparging on the air-water interfacial area and water saturation was investigated using a laboratory-scale sand packed column. It was found that water saturation decreases with decreasing surface tension of water until it reaches a point where this trend is reversed so that water saturation increases with further decrease in the surface tension. The lowest water saturation of 0.58 was achieved at a surface tension of 45.4 dyn/cm, which is considered as the optimum surface tension for maximum de-saturation for the initially water-saturated sand used in this study. The air-water contact area generated in the sand column due to air sparging was measured using a gaseous interfacial tracer, n-decane, and was found to monotonically increase with decreasing water saturation. The results of this study provide useful design information for surfactant-enhanced air sparging removal of volatile contaminants from aquifers.